Steroidal compounds and methods for obtaining the same



\ Patented July 31, was

UNITED STATES PATENT. OFFICE s'rsm'omu.

2,380,483 COMPOUNDS AND METHQDS FOR OBTAINING THE SAME l'arkqnavis &Company. De

' Romeo 1:. Wagner, suite College,

poration of Mlchitan No Drawing Application my 15, 1,944,

. Serial No. 535,150

1%., We: to trait, Mich, a cor-- 4 Ciaims. (CI- ZOHM-l) This inventionrelates to the'preparation'oi new compounds of the pregnane series whichare oxygenated in the nuclear position '12. These compounds are usefulintermediates in the preparation of hormone products.

In the copending Patent No. 3,352,052, issued July 4, 1944, a method wasdescribed by which steroidal sapogenins may be isomerized topseudosapogenins and these pseudo-sapogenin's further where S representsthe rings A, B- and C o! the steroid nucleus and R is an acyl radical(R20 representing an acyl anhydride) v This series or reactions may alsobe applied to the newly discovered steroidal .sapogenin kammo genin,described in J. Am. Chem. Soc., 65, 1199 r (1943) which may be describedas 2-hydroxy-l2- keto diosgenim The conversion of this topseudokammogenin is described in copending amfli tion, Serial No.535,751 flied May 15, 1944.

The invention may be illustrated as follows: Five grams ofpseudo-karnmogenin triaoetate, M. P. 147-8 is suspended in 150 cc.glacial metic acid and a solution of 3 gr. 0! chromic anhydride in 60cc. oi! 50% acetic'acid added at room temperature. After standing onehour sodium bisulfite solution is added, the solution diluted to oneliter with water and thoroughly extracted with ether.

The ether extract, after washing with dilute alkali and with water, isevaporated and the residue boiled 1 hour with. 5% alcoholic KOH. Onriilu- 'tion oi the alcohol white crystals areformed melting about 250which on acetylation yield 9. discstate, M. 1?. about 227. This productis 2,3-dihydroxy-mgo-diketmdlfl-presnadien.

while he oxidizing ent described, chromic acid in acetic acid at roomtemperature, is the preferred agent for carrying out this step otheragents capable of rupturing a carbon-carbon double bond may also be usedfor example ozone, per-acids and their salts and the like. Thetransformations described my be illustrated as follows:

b CHI CH1CH| l- 0H: on-c CH-CH:

2.01%: were cm omom EH-CH:

.gmm

Oxidation l and Hydrolysis GE: t CHI CH; =0

Aoetylation 2, a-dihydroxy-l Bildiketo-ii,lblane. M. I. about 250 C.

What]: claim is: 0H

1. A compound of the formula.

CH 0 CH (11:0 5 and groups hydrolyzable to V 01! Y W H H 2.5,16-pmgnadien-23-dlo1-12,20-dione.

, m 3. 5,16-pregnad1en-2,3-diol-12,20-d1one diacylates; 4.5,16-pregnadien-2,3-diol-12,20-dione discetate. where Y is a. member ofthe class'oomprising ROMEO B. WAGNER.

